TWI787686B - Alkoxycarbonylation of trivinylcyclohexane - Google Patents

Abstract

Process for the alkoxycarbonylation of trivinylcyclohexane.

Description

Alkoxycarbonylation of Trivinylcyclohexane

The present invention relates to a process for the alkoxycarbonylation of trivinylcyclohexane.

Alkoxycarbonylation of ethylenically unsaturated compounds is an increasingly important process. Alkoxycarbonylation is understood to mean the reaction of ethylenically unsaturated compounds, such as olefins, with carbon monoxide and alcohols in the presence of metals or metal complexes and ligands to form the corresponding esters:

The problem to be solved by the present invention is to provide a method for alkoxycarbonylation of trivinylcyclohexane. By using this method, all three vinyl groups can be converted to esters. Furthermore, it is intended to provide a fast-gelling plasticizer for plastics, in particular for PVC, which enables low processing temperatures.

This object is achieved by a method according to claim 1.

b)   加入配位基(L )和包含Pd的化合物， 或加入包含Pd和該配位基(L )的錯合物：

c)   加入具有1至12個碳原子的醇； d)   進料CO； e)   加熱a)至d)的反應混合物，其中將a)的該化合物/該混合物轉化為三酯。The method comprises the following method steps: a) first feeding one of compounds ( i ), ( ii ), ( iii ) or a mixture of at least two of these compounds:

b) Adding a ligand ( L ) and a compound comprising Pd, or adding a complex comprising Pd and the ligand ( L ):

c) adding an alcohol having 1 to 12 carbon atoms; d) feeding CO; e) heating the reaction mixture of a) to d), wherein the compound/the mixture of a) is converted into a triester.

In a variant of the process, the compound ( i ) is first fed in process step a).

In a variant of the process, the compound ( ii ) is first fed in process step a).

In a variant of the process, the alcohol in process step c) does not contain any other heteroatoms other than oxygen and does not contain multiple bonds.

In a variant (variant) of this method, wherein the alcohol in method step c) is selected from: Methanol, ethanol, n-butanol, methyl propanol, n-pentanol, isoamyl alcohol, 2-methylbutanol, 3-methylbutanol, n-hexanol, isohexanol, n-heptanol, isoheptanol, n- Octanol, Isooctyl Alcohol, 2-Ethylhexanol, n-Nonanol, Isononanol, n-Decanol, Isodecyl Alcohol, 2-Propylheptanol.

In a variant of the process, the alcohol in process step c) is methanol.

In a variant of the process, CO is fed in process step d) up to a pressure in the range of 20 bar to 60 bar.

In a variant of the process, CO is fed in process step d) up to a pressure in the range of 30 bar to 50 bar.

In a variant of the method, the heating in method step e) is performed at a temperature in the range from 90°C to 130°C.

In a variant of the process, the heating in process step e) is performed at a temperature in the range of 100°C to 120°C.

In a variant of this method, this method comprises an additional method step f): f) Purification of the triester.

In a variant of the process, the process comprises an additional process step g): g) reacting the purified triester with NaOMe and H ₂ to form a triol.

In a variant of the method, the reaction in method step g) is catalyzed with Ru-MACHO-BH.

In a variant of the process, the reaction in process step g) is carried out at a _H2 pressure in the range of 30 bar to 70 bar.

In a variant of the process, the reaction in process step g) is carried out at a _H2 pressure in the range of 40 bar to 60 bar.

In a variant of the process, the reaction in process step g) is carried out at a temperature in the range from 80°C to 120°C.

In a variant of the process, the reaction in process step g) is carried out at a temperature in the range from 90°C to 110°C.

In addition to the method, a compound is also claimed.

A kind of compound as claim item ( 1 )

The compound is preferably prepared as described herein.

Compounds prepared by the methods described above.

Hereinafter, the present invention will be described in detail by means of a working example.

Synthesis of trimethyl 3,3’,3”-(cyclohexane-1,2,4-triyl)tripropionate (1 ) (“Triesers”)

[Pd(acac) ₂ ] (15.2 mg, 0.1 mol%), L (103 mg, 0.4 mol%) and p-toluenesulfonic acid (PTSA, 143 mg, 1.5 mol%) were placed in 100 ml of steel under an argon atmosphere in an autoclave. Then, MeOH (30 ml) and trivinylcyclohexane (i) (8.1 g, 50 mmol) were injected by syringe. The autoclave was flushed 3 times with CO and then pressurized at 40 bar CO pressure. The reaction was carried out at 110°C for 10 hours. Subsequently, the autoclave was cooled to room temperature and depressurized. The desired product was purified by distillation (165°C, at 10 ⁻³ bar) and characterized by ¹ H-, ¹³ C-NMR and HR-MS (15.6 g, 91% yield).

¹ H-NMR (300 MHz, C ₆ D ₆ ) δ = 3.39-3.37 (m, 9H), 2.24-1.86 (m, 7H), 1.48-0.27 (m, 14 H). ¹³ C-NMR (75 MHz, C ₆ D ₆ ) δ = 173.68-173.54(m), 51.04, 40.60-40.47(m), 38.24, 38.14, 37.51, 37.07, 36.54, 36.10, 35.52, 35.14, 33.87, 32.70 、32.55、32.51、32.38、32.29、32.23、32.08、31.97、31.86、31.76、31.68、31.63、31.43、30.98、30.79、30.75、29.31、28.52、28.47、28.34、28.13、28.11、27.13、26.58、25.12、20.79 , 19.74. MS (EI): 311 (13.40), 293 (3.65), 269 (75.76), 237 (60.40), 219 (25.13), 205 (100), 191 (17.62), 177 (14.83), 145 (24.59). HR-MS (ESI): Calcd. for _{C18H30O6 [} M+H] ⁺ : _343.21152 , found: 343.21113.

Synthesis of 3,3',3"-(cyclohexane-1,2,4-triyl)tri(propan-1-ol) ( 2 ) (“triol”)

Ru-MACHO-BH (59 mg, 2 mol%) and NaOMe (27 mg, 10 mol%) were placed in a 25 ml steel autoclave under an argon atmosphere. Then, MeOH (8 ml) and triester ( 1 ) (1.93 g, 5.67 mmol) were injected by syringe. The autoclave was flushed 3 times with _H2 and then pressurized at 50 bar of _H2 pressure. The reaction was carried out at 100°C for 10 hours. Subsequently, the autoclave was cooled to room temperature and depressurized. The desired product was purified by filtration on silica gel and characterized by ¹ H-, ¹³ C-NMR and HR-MS (1.4 g, 96% yield).

¹ H-NMR (400 MHz, CD ₃ OD) δ = 3.32-3.30 (m, 6H), 1.85-1.77 (m, 2H), 1.63-0.62 (m, 19H). ¹³ C-NMR (100 MHz, CD ₃ OD) δ =63.53-63.29(m), 42.69, 42.53, 42.39, 42.31, 40.34, 40.24, 39.28, 38.89, 38.12, 38.02, 37.58, 37.27, 35.89, 34.78, 34.72 . MS(EI): 222(1.06), 194(1.14), 181(2.96), 163(11.54), 135(9.81), 121(17.04), 107(15.25), 93(32.69). HR-MS (ESI): Calcd. for _{C15H30O3 [} M+H] ⁺ : _259.22677 , found: 259.2269. Manufacture of plastisols

Manufacture of PVC plastisols, e.g. for the manufacture of surface coating films for floor coverings. The numbers in the plastisol formula are all in parts by mass. The formulations of the polymer compositions are listed in Table 1.

Weigh the liquid components first, then the powder components into PE beakers. The mixture was manually stirred with an ointment spatula so that no more unwetted powder remained. The mixing beaker is then clamped in the clamping device of the dissolution stirrer. After starting the stirrer, slowly increase the speed to about 2000 rpm. At the same time, the plastisol was carefully deaerated, keeping the pressure below 20 mbar.

Once the temperature of the plastisol reaches about 30°C, reduce the speed to about 350 rpm. Thereafter, the plastisol was degassed for 9 minutes at this speed and a pressure below 20 mbar. This ensures homogenization of the plastisol with a defined energy input. Thereafter, the plastisols were immediately equilibrated to 25.0 °C in a climate-controlled cabinet for further studies. Gelling properties of plastisols

The gelling properties of the pastes were measured in oscillatory mode with a Physica MCR 101 using a parallel plate analysis system (PP25) operating under shear stress control. To achieve even heat distribution and uniform sample temperature, an additional heating mantle is connected to the system.

Set the following parameters: Mode: Temperature Gradient Starting temperature: 25℃ Termination temperature: 180°C Heating/cooling rate: 5℃/min Oscillation frequency: 4-0.1 Hz logarithmic slope Cycle frequency Ω: 10 1/s Number of measurement points: 63 During measuring point: 0.5 min Automatic gap adjustment F: 0 N Constant measuring point period Gap width: 0.5 mm

Analysis program:

A few grams of the paste to be analyzed (free of air bubbles) is applied with a spatula to the lower plate of the analysis system. Doing this ensures that some paste can seep out of the assay system evenly (not more than 6 mm in any direction) after the assay system has been assembled. The heating mantle is then placed over the sample and analysis begins. The complex viscosity of the paste was measured after 24 h (the paste was stored at 25°C in Memmert temperature control cabinet) as a function of temperature.

A marked increase in complex viscosity is considered a measure of gelling. Therefore, the comparative value used is the temperature at which a paste viscosity of 1000 Pas is reached.

The experiment was repeated with three comparative plastisols, using in each case another plasticizer. Table 2: Temperature in °C at which the paste viscosity reaches 10 ³ Pa·s after 24 hours of gelation of the plastisol: experiment Plasticizer Gelling temperature[℃] 1* Trimethyl 3,3',3"-(cyclohexane-1,2,4-triyl)tripropionate (1) 65 2 Diisononyl phthalate (DINP), VESTINOL 9 from Evonik Performance Materials GmbH 83 3 Diisononyl 1,2-cyclohexanedicarboxylate (DINCH) from Evonik Performance Materials GmbH, ELATUR CH 101 4 Diisopentyl terephthalate (DPT), ELATUR DPT from Evonik Performance Materials GmbH 70 *Experiments were carried out with the compounds of the present invention

The target value of 1000 Pa*s can already be achieved at 65° C. with the compound (1) according to the invention. Such a low gelation temperature is beneficial to the processing procedure. They can process plastisols at lower temperatures.

Claims (13)

A method for the alkoxycarbonylation of trivinylcyclohexane, which comprises the following method steps: a) first feeding one of compounds ( i ), ( ii ), ( iii ) or at least two of these compounds mixture:

b) adding a ligand ( L ) and a compound comprising Pd, or adding a complex comprising Pd and the ligand ( L ):

c) adding an alcohol having 1 to 12 carbon atoms; d) feeding CO; e) heating the reaction mixture of a) to d), wherein the compound/the mixture of a) is converted into a triester. The method of claim 1, wherein the compound ( i ) is first charged in method step a). The method according to claim 1, wherein the compound ( ii ) is first charged in method step a). The method according to any one of claims 1 to 3, wherein the alcohol in method step c) does not contain any other heteroatoms other than oxygen and does not contain multiple bonds. The method as any one of claims 1 to 3, wherein the alcohol in method step c) is selected from: methanol, ethanol, n-butanol, methyl propanol, n-amyl alcohol, isoamyl alcohol, 2- Methylbutanol, 3-methylbutanol, n-hexanol, isohexanol, n-heptanol, isoheptanol, n-octanol, isooctyl alcohol, 2-ethylhexanol, n-nonanol, isononanol, n- Decanol, Isodecanol, 2-Propylheptanol. The method according to any one of claims 1 to 3, wherein the alcohol in method step c) is methanol. The process according to any one of claims 1 to 3, wherein CO is fed in process step d) up to a pressure in the range of 20 bar to 60 bar. The method according to any one of claims 1 to 3, wherein the heating in method step e) is at a temperature of 90°C to 130°C within the range. The method according to any one of claims 1 to 3, comprising the additional method step f): f) purifying the triester. The method of claim 9, which comprises an additional method step g): g) reacting the purified triester with NaOMe and H ₂ to generate triols. The method of claim 10, wherein the reaction in method step g) is catalyzed by Ru-MACHO-BH. The method as claimed in item 10, wherein the reaction in method step g) is carried out in the _H2 pressure range of 30 bar to 70 bar. The method according to claim 10, wherein the reaction in method step g) is carried out at a temperature ranging from 80°C to 120°C.